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| United States Patent |
5,232,701
|
|
Ogawa
, et al.
|
August 3, 1993
|
Boron carbonate and solid acid pesticidal composition
Abstract
A composition excellent in dispersibility and diffusion in water, and
storage stability comprising a) a pesticidal active ingredient, b) a
surface active agent, c) a carbonate, d) a solid acid and e) at least one
selected from the group consisting of boron oxide and metaboric acid,
wherein at least one of the carbonate and the solid acid is water-soluble,
the total content of the carbonate and the solid acid is in a proportion
of 5-90% to the total weight, the weight ratio of the carbonate to the
solid acid is in the range of 1:10-10:1, and the weight of at least one
selected from the group consisting of boron oxide and metaboric acid is in
a proportion of 0.5-40% to the total weight.
| Inventors:
|
Ogawa; Masao (Toyonaka, JP);
Ohtsubo; Toshiro (Sanda, JP);
Tsuda; Shigenori (Kyoto, JP)
|
| Assignee:
|
Sumitomo Chemical Company, Limited (Osaka, JP)
|
| Appl. No.:
|
774342 |
| Filed:
|
October 10, 1991 |
Foreign Application Priority Data
| Oct 11, 1990[JP] | 2-274984 |
| Jan 22, 1991[JP] | 3-022899 |
| Current U.S. Class: |
424/408; 424/409; 424/466; 424/489; 504/358 |
| Intern'l Class: |
A01N 025/12; A01N 055/08 |
| Field of Search: |
424/405,466,470,489
71/128,3
|
References Cited
U.S. Patent Documents
| 2773757 | May., 1953 | Connell et al. | 71/128.
|
| 3531278 | Sep., 1970 | Nies | 71/128.
|
| 4034038 | Jul., 1977 | Vogel | 260/462.
|
| 4933000 | Jun., 1990 | Somlo | 71/93.
|
| 5055305 | Oct., 1991 | Young | 424/466.
|
| Foreign Patent Documents |
| 3017639 | Nov., 1981 | DE.
| |
| 2579464 | Oct., 1986 | FR.
| |
| 45-24360 | Aug., 1970 | JP.
| |
| 47-27930 | Jul., 1972 | JP.
| |
| 50-20128 | Jul., 1975 | JP.
| |
| 51-88641 | Aug., 1976 | JP.
| |
| 55-2402 | Jan., 1980 | JP.
| |
| 59-030879 | Feb., 1984 | JP.
| |
| 62-164601 | Jul., 1987 | JP.
| |
| 2139893 | Nov., 1984 | GB.
| |
| 2184946 | Jul., 1987 | GB.
| |
| 9000007 | Jan., 1990 | WO.
| |
Other References
Chemical Abstracts, vol. 100, No. 26, Jun. 25, 1984, Columbus, Ohio, US;
abstract No. 215536Y, `Stable effervescent tablets` p. 345; & JP-A-59
030879 (Nissan Chemical Industries Ltd). Feb. 18, 1984.
|
Primary Examiner: Page; Thurman K.
Assistant Examiner: Levy; Neil
Attorney, Agent or Firm: Stevens, Davis, Miller & Mosher
Claims
What is claimed is:
1. A pesticidal composition comprising a) a pesticidal active ingredient,
b) a surface active agent, c) a carbonate, d) a solid acid and e) at least
one selected from the group consisting of boron oxide and metaboric acid,
wherein at least one of the carbonate and the solid acid is water-soluble,
the total content of the carbonate and the solid acid is in a proportion
of 5-9% to the total weight, the weight ratio of the carbonate to the
solid acid is in the range of 1:10-10:1, and the weight of at least one
selected from the group consisting of boron oxide and metaboric acid is in
a proportion of 0.5-40% to the total weight.
2. A pesticidal composition comprising a) a pesticidal active ingredient,
b) a surface active agent, c) a carbonate, d) a solid acid and e) boron
oxide, wherein at least one of the carbonate and the solid acid is
water-soluble, the total content of the carbonate and the solid acid is in
a proportion of 5-90% to the total weight, the weight ratio of the
carbonate to the solid acid is in the range of 1:10-10:1, and the weight
of the boron oxide is in a proportion of 0.5-40% to the total weight.
3. A pesticidal composition comprising a) a pesticidal active ingredient,
b) a surface active agent, c) a carbonate, d) a solid acid and e)
metaboric acid, wherein at least one of the carbonate and the solid acid
is water-soluble, the total content of the carbonate and the solid acid is
in a proportion of 5-90% to the total weight, the weight ratio of the
carbonate to the solid acid is in the range of 1:10-10:1, and the weight
of the metaboric acid is in a proportion of 0.5-40% to the total weight.
4. A composition according to claim 1, wherein a) is in a proportion of
0.01-80% by weight and b) is in a proportion of 0.1-70% by weight to the
total weight of the composition.
5. A composition according to claim 4, wherein the total weight of c) and
d) is in a proportion of 10-70% by weight to the total weight.
6. A composition according to claim 2, wherein the weight ratio of c) to d)
is in the range of 1:5-5:1.
7. A composition according to claim 2, wherein a) is in a proportion of
0.01-80% by weight and b) is in a proportion of 0.1-70% by weight to the
total weight of the composition.
8. A composition according to claim 3, wherein a) is in a proportion of
0.01-80% by weight and b) is in a proportion of 0.1-70% by weight to the
total weight of the composition.
9. A composition according to claim 7, wherein the total weight of c) and
d) is in a proportion of 10-70% by weight to the total weight.
10. A composition according to claim 8, wherein the total weight of c) and
d) is in a proportion of 10-70% by weight to the total weight.
Description
The present invention relates to fizzy granules and fizzy tablets
containing pesticide.
BRIEF DESCRIPTION OF FIGURE
FIG. 1 shows a VAT used in test example 2
As the fizzy granules and fizzy tablets containing pesticide, there have
hitherto been known those described in Japanese Examined Patent
Publication Nos. 24360/1970, 27930/1972 and 20128/75.
These formulations had problems such as poor stability during storage.
That is, both carbonates and solid acids are present in the conventional
formulations, which are observed to generate carbon dioxide gas due to the
absorption of moisture in air during their storage in a container such as
a kraft bag, a polyethylene bag or a polyethylene bottle and thus cause
the problem of decreasing the weight of the product. These formulations
also have problems such as the deterioration of disintegrability in water,
dispersibility in water or diffusion ability in water upon storage for a
long period. Furthermore, when these preparations are stored in a
polyethylene-laminated aluminium bag having no gas permeability, the bag
is often expanded by the generated carbon dioxide gas.
There is the danger of breaking the bag at the violent reaction.
In consideration of the states, the present inventors have found a fizzy
granules and fizzy tablets comprising a pesticidal active ingredient, a
surface active agent, a carbonate, a solid acid and at least one selected
from boron oxide and metaboric acid and having an excellent storage
stability.
The present invention relates to a pesticidal formulation (referred to
hereinafter as the composition of the present invention) comprising a) a
pesticidal active ingredient, b) a surface active agent, c) a carbonate,
d) a solid acid and e) at least one selected from boron oxide (B.sub.2
O.sub.3) and metaboric acid, wherein at least one of the carbonate and the
solid acid is water-soluble, the total content of the carbonate and the
solid acid is in a proportion of 5-90% to the total weight, the weight
ratio of the carbonate to the solid acid is in the range of 1:10-10:1, and
the weight of the boron oxide and/or metaboric acid is in a proportion of
0.5-40%, preferably 1-15% to the total weight.
In the composition of the present invention, the pesticidal active
ingredient used is not limited specifically and includes the following
compounds, active isomers thereof or mixtures thereof.
Typical compounds are listed together with the compound numbers in the
following:
(1) .alpha.-cyano-3-phenoxybenzyl 2-(4-chlorophenyl)-3-methylbutyrate,
(2) (S)-.alpha.-cyano-3-phenoxybenzyl
(S)-2-(4-chlorophenyl)-3-methylbutyrate,
(3) .alpha.-cyano-3-phenoxybenzyl
2,2,3,3-tetramethylcyclopropanecarboxylate,
(4) 3-phenoxybenzyl
3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,
(5) 3-phenoxybenzyl chrysanthemate,
(6) 3-phenoxybenzyl (1R)-chrysanthemate,
(7) .alpha.-cyano-3-phenoxybenzyl
3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,
(8) .alpha.-cyano-3-(4-bromophenoxy)benzyl
3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,
(9) .alpha.-cyano-3-(4-fluorophenoxy)benzyl
3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,
(10) .alpha.-cyano-3-(3-bromophenoxy)benzyl
3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,
(11) .alpha.-cyano-3-(4-chlorophenoxy)benzyl
3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,
(12) .alpha.-cyano-3-phenoxybenzyl chrysanthemate,
(13) .alpha.-cyano-3-phenoxybenzyl (1R)-chrysanthemate,
(14) .alpha.-cyano-3-(4-bromophenoxy)benzyl
2-(4-chlorophenyl)-3-methylbutyrate,
(15) .alpha.-cyano-3-(3-bromophenoxy)benzyl
2-(4-chlorophenyl)-3-methylbutyrate,
(16) .alpha.-cyano-3-(4-chlorophenoxy)benzyl
2-(4-chlorophenyl)-3-methylbutyrate,
(17) .alpha.-cyano-3-(4-fluorophenoxy)benzyl
2-(4-chlorophenyl)-3-methylbutyrate,
(18) .alpha.-cyano-3-phenoxybenzyl 2-(4-bromophenyl)-3-methylbutyrate,
(19) .alpha.-cyano-3-phenoxybenzyl 2-(4-tert-butylphenyl)-3-methylbutyrate,
(20) .alpha.-cyano-3-phenoxybenzyl
2-(3,4-methylenedioxyphenyl)-3-methylbutyrate,
(21) .alpha.-cyano-4-fluoro-3-phenoxybenzyl
3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,
(22) .alpha.-cyano-3-phenoxybenzyl
2-(2-chloro-4-trifluoromethylanilino)-3-methylbutyrate,
(23) .alpha.-cyano-3-phenoxybenzyl
2-(4-difluoromethoxyphenyl)-3-methylbutyrate,
(24) .alpha.-cyano-3-phenoxybenzyl
(S)-2-(4-difluoromethoxyphenyl)-3-methylbutyrate,
(25) .alpha.-cyano-(5-phenoxy-2-pyridyl)methyl
3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,
(26) .alpha.-cyano-3-phenoxybenzyl
2,2-dimethyl-3-(1,2,2,2-tetrabromoethyl)cyclopropanecarboxylate,
(27) .alpha.-cyano-3-phenoxybenzyl
2,2-dimethyl-3-(1,2-dichloro-2,2-dibromoethyl)cyclopropanecarboxylate,
(28) .alpha.-cyano-3-phenoxybenzyl
1-(4-ethoxyphenyl)-2,2-dichlorocyclopropanecarboxylate,
(29) .alpha.-cyano-3-phenoxybenzyl
2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate,
(30) 2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether,
(31) 2-(4-ethoxyphenyl)-3,3,3-trifluoropropyl 3-phenoxybenzyl ether,
(32) 2-methyl-3-phenylbenzyl (1R,
trans)-2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxy
late,
(33) 2,3,5,6-tetrafluoro-4-methylbenzyl (1R,
trans)-2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxy
late,
(34) 3,4,5,6-tetrahydrophthalimidomethyl chrysanthemate,
(35) 3,4,5,6-tetrahydrophthalimidomethyl (1R)-chrysanthemate,
(36) 3-allyl-2-methyl-4-oxocyclopent=2-enyl chrysanthemate,
(37) 3-allyl-2-methyl-4-oxocyclopent-2-enyl (1R)-chrysanthemate,
(38) (S)-2-methyl-4-oxo-3-(2-propynyl)cyclopent-2-enyl (1R)-chrysanthemate,
(39) 1-ethynyl-2-methyl-2-pentenyl (1R)-chrysanthemate,
(40) 5-benzyl-3-furylmethyl chrysanthemate,
(41) 5-benzyl-3-furylmethyl (1R)-chrysanthemate,
(42) .alpha.-cyano-3-(4-bromophenoxy)benzyl
3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate,
(43) O,O-dimethyl O-(3-methyl-4-nitrophenyl) phosphorothioate,
(44) O,O-dimethyl S-[1,2-di(ethoxycarbonyl)ethyl] phosphorodithioate,
(45) O,O-dimethyl O-(4-cyclophenyl) phosphorothioate,
(46) O,O-dimethyl S-(.alpha.-ethoxycarbonylbenzyl) phosphorodithioate,
(47) O,O-diethyl O-(2-isopropyl-4-methyl-6-pyrimidinyl) phosphorothioate,
(48) O,O-dimethyl O-[3-methyl-4-(methylthio)phenyl] phosphorothioate,
(49) O-(4-bromo-2,5-dichlorophenyl) O,O-diethylphosphorothioate,
(50) 2-methoxy-4H-1,3,2-benzoxaphosphorin-2-sulfide,
(51) O,O-dimethyl O-(2,4,5-trichlorophenyl) phosphorothioate,
(52) O,O-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate,
(53) O,O-dimethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate,
(54) O,O-dimethyl O-(4-bromo-2,5-dichlorophenyl) phosphorothioate,
(55) dimethyl 2,2-dichlorovinylphosphate,
(56) O,S-dimethyl N-acetylphosphoroamidothioate,
(57) O-(2,4-dichlorophenyl) O-ethyl S-propyl phosphorodithioate,
(58) O,O-dimethyl S-(5-methoxy-1,3,4-thiadiazolin-2-on-3-ylmethyl)
phosphorodithioate,
(59) dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate,
(60) O-ethyl O-(4-nitrophenyl) benzenephosphonothioate,
(61) O,O-dimethyl S-(N-methylcarbamoylmethyl) phosphorodithioate,
(62) 2-sec-butylphenyl N-methylcarbamate,
(63) 3-methylphenyl N-methylcarbamate,
(64) 3,4-dimethylphenyl N-methylcarbamate,
(65) 2-isopropoxyphenyl N-methylcarbamate,
(66) 1-naphthyl N-methylcarbamate,
(67) 2-isopropylphenyl N-methylcarbamate,
(68) O,O-diethyl S-[2-(ethylthio)ethyl]phosphorodithioate,
(69) S-methyl N-[(methylcarbamoyl)oxy]thioacetoimidate,
(70)
trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxothiazolidin-3-carboxam
ide,
(71) 2,3-dihydro-2,2-dimethyl-7-benzofuranyl
N-dibutylaminothio-N-methylcarbamate,
(72) N,N-dimethyl-1,2,3-trithian-5-ylamine,
(73) 1,3-bis(carbamoylthio)-2-(N,N-dimethylamino)-propane hydrochloride,
(74) ethyl
N-[2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl(methyl)aminothio]-N-
isopropyl-.beta.-alaninate,
(75)
1-[3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl]-3-(2,6-
difluorobenzoyl)urea,
(76) 1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea,
(77)
1-[3,5-dichloro-4-(1,1,2,2-tetrafluoroethoxy)-phenyl]-3-(2,6-difluorobenzo
yl)urea,
(78) ethyl 2-(4-phenoxyphenoxy)ethylcarbamate,
(79) 2-tert-butyl-5-(4-tert-butylbenzylthio)-4-chloropyridazin-3(2H)-one,
(80)
1-[4-(2-chlor-4-trifluoromethylphenoxy)-2-fluorophenyl]-3-(2,6-difluoroben
zyl)urea,
(81) tert-butyl
(E)-.alpha.-(1,3-dimethyl-5-phenoxypyrazol-4-ylmethyleneaminoxy)-p-toluate
(82)
3,7,9,13-tetramethyl-5,11-dioxa-2,8,14-trithia-4,7,9,12-tetraazapentadeca-
3,12-diene-6,10-dione,
(83) 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylidenamine,
(84) 5-ethoxy-3-trichloromethyl-1,2,4-triadiazole,
(85) O,O-diisopropyl S-benzyl phosphorothiolate,
(86) O-ethyl S,S-diphenyl dithiophosphate,
(87) Polyoxin,
(88) Blastocidine S,
(89) 3,4-dichloropropionanilide,
(90) isopropyl N-(3-chlorophenyl)carbamate,
(91) S-ethyl N,N-dipropylthiolcarbamate,
(92) 3-methoxycarbonylaminophenyl N-(3-methylphenyl)carbamate,
(93) N-methoxymethyl-2-chloro-2',6'-diethylacetanilide,
(94) 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline,
(95) S-(4-chlorobenzyl) N,N-diethylthiolcarbamate,
(96) S-ethyl N,N-hexamethylenethiolcarbamate,
(97)
N-(1,1,3-trimetyl-2-oxa-4-indanyl)-5-chloro-1,3-dimethylpyrazol-4-carboxya
mide,
(98) 3'-isopropoxy-2-(trifluoromethyl)benzanilide,
(99) diisopropyl 1,3-dithiolan-2-ilidenemalonate,
(100) 1,2,5,6-tetrahydropyrrolo[3,2,1-i,j]quinolin-4-one,
(101) 3-allyloxy-1,2-benzoisothiazole-1,1-dioxide,
(102) 5-methyl[1,2,4]triazolo[3,4-b]benzothiazole,
(103) 1,2-bis(3-methoxycarbonyl-2-thioureido)benzene,
(104) 1-(4-chlorobenzyl)-1-cyclopentyl-3-phenylurea,
(105) Validamycin A
(106) 6-(3,5-dichloro-4-methylphenyl)-3(2H)-pyridazinone,
(107) Kasugamycin hydrochloride,
(108) Methyl 1-(butylcarbamoyl)benzimidazole-3-carbamate,
(109)
3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide,
(110) 3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione,
(111) manganese ethylenebisdithiocarbamate,
(112) manganese and zinc ethylenebisdithiocarbamate,
(113) N-(trichloromethylthio)cyclohex-4-en-1,2-dicarboximide,
(114) 3'-isopropoxy-2-methylbenzanilide,
(115) 3-hydroxy-5-methylisoxazole,
(116) tetrachloroisophthalonitrile,
(117) 1,1'-iminodi(octamethylene)diguanidine,
(118) 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butanone,
(119)
(E)-4-chloro-2-(trifluoromethyl)-N-[1-(imidazol-1-yl)-2-propoxyethylidene]
aniline,
(120) methyl N-(methoxyacetyl)-N-(2,6-dimethylphenyl)-alaninate,
(121)
3-chloro-N-(3-chloro-5-trifluoromethyl-2-pyridyl)-2,6-dinitro-4-methylanil
ine,
(122) N-butoxymethyl-2-chloro-2',6'-diethylacetanilide,
(123) O-ethyl O-(5-methyl-2-nitrophenyl)-sec-butyl phosphoroamidethioate,
(124) ethyl N-chloroacetyl-N-(2,6-diethylphenyl)-glycinate,
(125) 2-[1-methyl-2-(4-phenoxyphenoxy)ethoxy]pyridine,
(126)
(E)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)-1-penten-3-o
l,
(127)
1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4(triazol-1-yl)-1-pentan-3-ol,
(128) 2-bromo-N-(.alpha.,.alpha.-dimethylbenzyl)-3,3-dimethylbutanamide,
(129) 1-(1-methyl-1-phenylethyl)-3-(p-tolyl)urea,
(130) 2-(2-naphthoxy)propionanilide,
(131) 2-(2,4-dichloro-3-methylphenoxy)propionanilide,
(132) 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-pyrazolyl p-toluenesulfonate,
(133) 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-phenacyloxypyrazole,
(134)
4-(2,4-dichloro-3-methylbenzoyl)-1,3-dimethyl-5-(4-methylphenacyloxy)pyraz
ole,
(135) 2,4,6-trichlorophenyl 4-nitrophenyl ether,
(136) 2,4-dichlorophenyl 3-methoxy-4-nitrophenyl ether,
(137) 2,4-dichlorophenyl 3-methoxycarbonyl-4-nitrophenyl ether,
(138) 2-benzothiazol-2-yloxy-N-methylacetanilide,
(139) 2',3'-dichloro-4-ethoxymethoxybenzanilide,
(140)
5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazol-2(3H)-one
(141) 2-amino-3-chloro-1,4-naphthoquinone,
(142) methyl
2-[3-(4,6-dimethoxypyrimidin-2-yl)-ureidosulfonylmethyl]benzoate,
(143) 3,7-dichloroquinoline-8-carboxylic acid,
(144) ethyl
5-[3-(4,6-dimethoxypyrimidin-2-yl)ureidosulfonyl]-1-methylpyrazole-4-carbo
xylate,
(145)
3-chloro-2-[4-chloro-2-fluoro-5-(2-propionyloxy)phenyl]-4,5,6,7-tetrahydro
-2H-indazole,
(146) O-(4-tert-butylphenyl)
N-(6-methoxy-2-pyridyl)-N-methylthionocarbamate,
(147) O-(3-tert-butylphenyl)
N-(6-methoxy-2-pyridyl)-N-methylthionocarbamate,
(148) O-(4-chloro-3-ethylphenyl)
N-(6-methoxy-2-pyridyl)-N-methylthionocarbamate,
(149) O-(4-bromo-3-ethylphenyl)
N-(6-methoxy-2-pyridyl)-N-methylthionocarbamate,
(150) O-(3-tert-bytyl-4-chlorophenyl)
N-(6-methoxy-2-pyridyl)-N-methylthionocarbamate,
(151) O-(4-trifluoromethylphenyl)
N-(6-methoxy-2-pyridyl)-N-methylthionocarbamate,
(152) 1-(2-chlorobenzyl)-3-(.alpha.,.alpha.-dimethylbenzyl)-urea,
(153) N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,
(154) O-(2,6-dichloro-4-methoxyphenyl) O,O-dimethyl phosphorothioate,
(155) 1-ethyl-1,4-dihydro-6,7-methylenedioxy-4-oxo-3-quinolinecarboxylic
acid,
(156)
(E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)-1-penten
-3-ol,
(157) isopropyl 3,4-diethoxyphenylcarbamate,
(158)
N-[4-chloro-2-fluoro-5-(1-methyl-2-propynyloxy)phenyl]-3,4,5,6-tetrahydrop
hthalimide,
(159)
N-[4-chloro-2-fluoro-5-(pentyloxycarbonylmethoxy)phenyl]-3,4,5,6-tetrahydr
ophthalimide,
(160)
7-fluoro-6-(3,4,5,6-tetrahydrophthalimide)-4-(2-propynyl)-3,4-dihydro-1,4-
benzoxazin-3(2H)-one,
(161)
2-[1-(ethoxyimino)ethyl]-3-hydroxy-5-[2-[4-(trifluoromethyl)phenylthio]eth
yl]-2-cyclohexen-1-one,
(162) 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea,
(163) isopropyl (2E,4E)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate,
(164)
2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadia
zin-4-one,
(165) 2-phenoxy-6-(neopentyloxymethyl)pyridine,
(166)
3-chloro-2-[7-fluoro-4-(2-propynyl)-3,4-dihydro-1,4-benzoxazin-3(2H)-on-6-
yl]-4,5,6,7-tetrahydro-2H-indazole,
(167) 4'-chloro-2'-(.alpha.-hydroxybenzyl)isonicotinanilide,
(168) 6-(benzylamino)pyrine,
(169) 5-chloro-3-methyl-4-nitro-1H-pyrazole,
(170) 2-chloroethyltrimethylammonium chloride,
(171) 2-(3-chlorophenoxy)propionic acid,
(172) 3-(4-chlorophenyl)-1,1-dimethylurea,
(173) 2,4-dichlorophenoxyacetic acid,
(174) 3-(3,4-dichlorophenyl)-1,1-dimethylurea,
(175) 1,1'-ethylene-2,2'-bipyridinium dibromide,
(176) maleic hydrazide,
(177) 2,4-dinitro-6-sec-butylphenol,
(178) 2,4-dimethyl-5-(trifluoromethylsulfonylamino)-acetanilide,
(179) 6-(furfurylamino)purine,
(180) .beta.-hydroxyethylhydrazine,
(181) 3-indoleacetic acid,
(182) 3-methyl-5-(1-hydroxy-4-oxo-2,6,6-trimethyl-2-cyclohexen-1-yl) cis,
trans-2,4-pentadienic acid,
(183) 1-naphthoxyacetic acid,
(184) 7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid monoalkylamine salt,
(185) 1-phenyl-3-[4-(2-chloropyridyl)]urea,
(186) sodium 5-chloro-1H-indazol-3-ylacetate,
(187) S,S-dimethyl 2-(difluoromethyl)-4-(2-methylpropyl)-6
-(trifluoromethyl)pyridine-3,5-dicarbothioate
(188)
3-(4,6-dimethoxy-1,3,5-triazin-2-yl)-1-[2-(2-methoxyethoxy)phenylsulfonyl]
urea,
(189)
exo-1-methyl-4-(1-methylethyl)-2-(2-methylphenylmethoxy)-7-oxabicyclo[2.2.
1]heptane,
(190) 2',6'-diethyl-N-[(2-cis-butenoxy)methyl]2-chloroacetanilide,
(191) 2,3-dihydro-3,3-dimethyl-5-benzofuranyl ethanesulfonate,
(192) 2',6'-dimethyl-N-(3-methoxy-2-thenyl)-2-chloroacetanilide,
(193)
1-(2-chloroimidazo[1,2-a]pyridin-3-ylsulfonyl)-3-(4,6-dimethoxy-2-pyrimidi
nyl)urea,
(194) 3-isopropyl-1H-2,1,3-benzothiadiazin-4-(3H)-one-2,2-dioxide,
(195)
2-(1-ethoxyiminobutyl)-5-[2-(ethylthio)propyl]-(3-hydroxycyclohex-2-en-1-o
ne, 2',6'-diethyl-N-(2-propoxyethyl)-2-chloroacetanilide,
(196) 2',6'-diethyl-N-(2-propoxyethyl)-2-chloroacetanilide,
(197) 1,1'-dimethyl-4,4'-bipyridinium dichloride,
(198) S-(1-methyl-1-phenylethyl) piperidine-1-carbothioate,
(199) S-(2-methyl-1-piperidinecarbonylmethyl) O,O-dipropyl dithiophosphate,
(200) S-behzyl N-ethyl-N-(1,2-dimethylpropyl)thiolcarbmate,
(201) 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine,
(202) 2-methylthio-4,5-bis(ethylamino)-1,3,5-triazine,
(203) ammonium homoalanin-4-yl(methyl)phosphinate,
(204) 2-chloro-4,6-bis(ethylamino)-1,3,5-triazine,
(205) sodium
L-2-amino-4-[(hydroxy)(methyl)phosphinoyl]butyryl-L-alanyl-L-alaninate,
(206) isopropylammonium N-(phosphonomethyl)glycinate,
(207) trimethylsulfonium N-(phosphonomethyl)glycinate,
(208) 2-methylthio-4-ethylamino-6-(1,2-dimethylpropylamino)-1,3,5-triazine,
(209) succinic 2,2-dimethylhydrazide, and
(210) 3-[2-(3,5-dimethyl-2-oxocyclohexyl)-2-hydroxymethyl]glutarimide.
In the composition according to the present invention, the addition of a
calcined product precipitated hydrated silicon dioxide produced by the wet
process or a silica produced by the dry process is preferred when the
active ingredient has a melting point of lower than 70.degree. C. That is,
additives such as water-soluble carriers, water-soluble polymers, mineral
carriers, solvents, lubricants or disintegrating agents are incorporated
in addition to the essential active ingredient, the surface active agent,
the carbonate, the solid acid and boron oxide and/or metaboric acid
according to necessity.
In the composition according to the present invention, the pesticidal
active ingredients may be used alone or in admixture of the two or more of
them with an optional mixing ratio. The contents of these active
ingredients vary depending on the kinds of the ingredients and are in the
range of 0.01-80% by weight, preferably 0.1-50% by weight in proportion to
the total weight of the composition of the present invention. In addition,
when these active ingredients are liquids or are employed in the form of a
solution in a solvent, the calcined product of precipitated hydrated
silicon dioxide produced by the wet process or the silica produced by the
dry process exhibit only insufficient effect as an oil absorbing agent at
a content of the liquid ingredient containing the solvent exceeding 60% by
weight to the total weight of the composition of the present invention.
Thus, the content of the liquid ingredient should be usually in the range
of 0.01-60% by weight, preferably 0.1-40% by weight.
The amount added to the calcined product of precipitated hydrated silicon
dioxide produced by the wet process or the silica produced by the dry
process is usually in the range of 50-200% by weight, preferably 60-100%
by weight to the total liquid ingredient which is a liquid active
ingredient or a solution in a solvent. For example, a synthetic hydrated
silicon dioxide (silica produced by the wet process) such as Tokusil G-UN,
Tokusil P, Tokusil U, Tokusil N (manufactured by Tokuyama Soda Co., Ltd.),
Carplex #80 (manufactured by Shionogi & Co., Ltd.) Carplex #67, Carplex
#1120, Carplex #100, Carplex #22S, Carplex FPS-1, Carplex FPS-2, Carplex
FPS-3, Carplex FPS-4, Nipsil (manufactured by Nippon Silica) or Ultrasil
(manufactured by Degussa) calcined at a temperature of
700.degree.-900.degree. C., preferably 800.degree.-900.degree. C. is used
as a calcined product of a silica produced by the wet process.
Commercially available products such as Carplex CS-5, Carplex CS-7 or
Finisil P-8 (manufactured by Tokuyama Soda Co., Ltd.) may be used as such.
On the other hand, as a silica produced by the dry process, there is
employed a light silicic anhydride such as AEROSIL 200 or AEROSIL 300
(manufactured by Degussa).
Furthermore, when the active ingredient has a melting point in the range of
0.degree.-70.degree. C., a solvent is added, if necessary, in order to
decrease the viscosity of the ingredient at its production and to prevent
the crystallization of the active ingredient upon storage at a low
temperature. As the solvent, there is usually used a non-volatile or
sparingly volatile organic solvent. The solvents used for regulating
viscosity and preventing crystallization of the active ingredients include
those which are homogeneously mixed with the active ingredients, for
example, aromatic hydrocarbons such as phenylxylethane ketones, negetable
oils, mineral oils, liquid paraffin, polyethylene glycol having an average
molecular weight in the range of about 200-600 which is liquid at room
temperature, polypropylene glycol, and glycol ether such as polypropylene
glycol methyl ether and acetate thereof, particularly phenylxylylethane,
glycol ethers and acetates of glycol ethers are preferred.
The added amount of the solvent is usually in the range of 10-1000% by
weight, preferably 30-200% by weight to the amount of the active
ingredient. The aforementioned solvent may be added, if necessary, for
lowering the viscosity at production, even if the active ingredient has a
melting point of 0.degree. C. or less.
As the surface active agents used in the present invention, there can be
mentioned anionic surface active agents such as alkyl aryl sulfonates,
alkyl naphthalene sulfonates, lignin sulfonates, dialkyl sulfosuccinates,
polyoxyethylene alkyl aryl ether sulfates, alkali metal salts of
copolymers having carboxyl groups and fatty acid salts and noinoic surface
active agents such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl
phenyl ethers, polyoxyethylene styryl phenyl ethers, polyoxyethylene alkyl
esters, sorbitan alkyl esters and polyoxyethylene sorbitan alkyl esters
which are able to emulsify and disperse the active ingredient and the
calcined silica according to the wet process. Also, there may be used
cathionic surface active agents, or amphoteric surface active agents
according to necessity. These surface active agents are used alone or in
admixture of the two or more. The used amount of the surface active agent
is usually in a proportion of 0.1-70% by weight, preferably 1-40% by
weight, more preferably 3-20% by weight, to the total weight of the
composition of the present invention.
As the carbonate used in the composition of the present invention, there
are mentioned for example sodium carbonate, potassium carbonate, lithium
carbonate, ammonium carbonate, calcium carbonate, sodium bicarbonate,
potassium bicarbonate, lithium bicarbonate, ammonium bicarbonate,
potassium sesquicarbonate and ammonium sesquicarbonate. Sodium bicarbonate
or sodium carbonate is particularly preferred. The aforementioned
carbonates are used alone or as a mixture of the two or more at any
ratios.
As the solid acid used in the composition of the present invention, there
are mentioned for example citric acid, succinic acid, maleic acid, fumaric
acid, tartaric acid, oxalic acid, malonic acid, malic acid, adipic acid,
boric acid, sodium dihydrogen phosphate, potassium dihydrogen phosphate,
benzoic acid, sulfamic acid, salicylic acid, ascobic acid, glutamic acid,
asparatic acid, sorbic acid, nicotinic acid and phenylacetic acid.
Particularly, maleic acid, fumaric acid, citric acid, succinic acid, boric
acid, malic acid and tartaric acid are preferred. These acids are used
alone or as a mixture of the two or more at any ratios.
The total amount of the carbonate and the solid acid used is usually in a
proportion of 5-90% by weight, preferably 10-70% by weight, more
preferably 20-60% by weight to the total weight of the composition of the
present invention. The weight ratio of the carbonate to the solid acid is
usually in a range of 1:10-10:1, preferably 1:5-5:1, more preferably
1:3-3:1.
Boron oxide and metaboric acid used in the present invention can be used
alone or as a mixture of the two or more at any ratios.
Also, as the water-soluble carrier, the water-soluble polymer, the mineral
carrier, the lubricant and the disintegrating agent, there are mentioned
the following materials.
First of all, as the water-soluble carrier, there are mentioned urea,
lactose, ammonium sulfate, sugar, sodium chloride and sodium sulfate.
As the water-soluble polymer, there are mentioned hydroxypropyl cellulose,
methyl cellulose, methylethyl cellulose, polyvinyl alcohol, polyvinyl
pyrrolidone, hydroxypropylmethyl cellulose, sodium carbonxymethyl
cellulose, and polyethylene glycols having an average molecular weight of
6000-20000.
As the mineral carrier, there are mentioned kaolin clay, diatomite, acid
clay, talc and attapulgite clay.
Moreover, the lubricant includes magnesium stearate, or titanium oxide, and
the disintegrating agent includes microcrystalline cellulose.
When these water-soluble carrier, water-soluble polymer, mineral carrier,
lubricant and disintegrating agent are added, the amount added is usually
in a proportion of 0.1-50% by weight, preferably 0.5-20% by weight to the
total weight of the composition of the present invention.
Furthermore, it is also possible to add appropriately a stabilizer, an
effect stimulating agent, a colorant, a perfume, or a builder to the
composition of the present invention.
The composition according to the present invention, of which active
ingredient has a melting point of 70.degree. C. or more, can be produced
by pulverizing the active ingredient alone or a mixture of it with either
one or all of the surface active agent, the carbonate and the solid acid
with a dry pulverizer such as air mill, pinmill or hammer mill, and then
mixing them with the residual ingredients. When the active ingredient is
liquid or in the form of liquid by the addition of a solvent, the
composition may be produced in the same manner as above after the active
ingredient is absorbed into the calcined product of silica produced by the
wet process or the silica produced by the dry process.
The powderous composition of the present invention obtained thus can be
used as such, but it is desirable to us it in the form of granule or
tablet in consideration of its handling, safety or environmental effect.
In this connection, the granule means the granulated product of the
powderous composition of the present invention, of which shape varies
depending on granulation methods and is in a wide range of cylindricals,
sphericals or irregulars. Also, the tablet means a product of the
powderous or glanular composition of the present invention compressed into
a certain shape, which is in a variety from the ones having sharp edges or
rounded edges to the one of a lens having shallow curvature, such as a
pillow shape, an almond shape, a finger shape, triangle, square, pentagon
or a capsule shape.
The granule can be prepared by forming the powderous composition of the
present invention into a granulated product in the form of sheet, pillow
or slugs with a dry granulating machine such a roll compactor or a
briquetting machine or with a slug machine, respectively, and breaking the
granulated product or slugs with a screening apparatus. In this
connection, the granule is preferably subjected to sphering treatment with
a Marumerizer (Produced by Fuji Paudal Co., Ltd.) or the like in order to
prevent dusting on its transport or use. If the compacting machine is
used, the powderous composition is placed between rotary rolls and is
pressed at 30 kg/cm.sup.2 or more, preferably 50 kg/cm.sup.2 or more. This
method uses no water, and carbon dioxide gas is not generated during the
production process, so that when the granule is applied to a paddy field,
a pond or a river or diluted with water, effervescence is observed more
sufficiently.
The aforementioned granule has usually a particle diameter in the range of
about 10000-100 .mu.m, preferably about 4000-297 .mu.m.
The tablet may be prepared by tableting a certain amount of the powderous
composition of the present invention by hand. In an industrial scale,
tablets having a certain weight can be continuously prepared by tableting
the aforementioned powder or granule in a tableting machine or a
briquetting machine.
The tablet may be in the sizes suitable for its applications and usually
has a diameter in the range of about 7-60 mm, a thickness in the range of
about 1-40 mm and a weight in the range of about 0.1-100 g, preferably
about 1-50 g.
The composition of the present invention is directly applied to an
irrigated paddy field, a river, a pond, a field, a lawn, an orchard, a
non-cultivated field, or it is used as an appropriate dilution with water.
When the composition of the present invention is applied to an irrigated
paddy field, the applied amount thereof varies depending on the kinds or
amounts of the active ingredients and is usually in the range of about
50-2000 g, preferably about 500-1000 g per 10 are.
When the composition of the present invention is applied directly, no
special devices are generally required. For instance, an operator gets
into a paddy field and applies the composition of the present invention
uniformly or to one or more places of the paddy field, or he applies the
composition to the sides of the footpaths of the paddy field or to the
water inlet of the paddy field or distributes the composition from the
footpaths without getting into the paddy field, so that the active
ingredient can be distributed and diffused to all of the paddy field.
Also, the composition can be applied by a motorized granular application
at a footpath or dispersed into air with a helicopter, an airplane or a
radiocontrolled airplane.
When the composition of the present invention is applied to an irrigated
paddy field, a pond or a river, it moves by the generation of carbon
dioxide gas and the active ingredient is rapidly and uniformly diffused
into water. Thus the pesticidal ingredient against pests, harmful
microorganisms or weeds exhibits sufficient effects on pests or crops,
respectively, and is diffused uniformly, so that the composition of the
present invention is also a composition excellent in the point of reducing
the phytotoxicity of pesticides. Also, when the composition of the present
invention is applied to a paddy field, the applied amount thereof can be
reduced extensively, so that the composition is also useful in the points
of the production, transport, storage and labor-saving dispersion of the
product. Furthermore, when the composition of the present invention is
used as a dilution with water, it generates carbon dioxide gas in water
and thus is disintegrated, dispersed or emulsified easily, so that it can
be handled conveniently.
The present invention is further explained in detail with reference to
preparation examples, comparative examples and test examples, but it is
not limited thereto. In addition, parts in the preparation examples and
the comparative examples indicate parts by weight.
First of all, preparation examples are described.
PREPARATIVE EXAMPLE 1
20 parts of the compound (128), 4.5 parts of REAX 85A (sodium lignin
sulfonate, manufactured by Westvaco), 0.5 part of REAX 88B (sodium lignin
sulfonate, manufactured by Westvaco), 5 parts of GEROPON SC-211 (potassium
salt of a copolymer having carboxyl groups, manufactured by Rhone
Poulenc), 10 parts of boron oxide, 30 parts of sodium carbonate and 30
parts of maleic acid were mixed well in a juice mixer and then pulverized
in a centrifugal pulverizer. The mixture was next granulated into a
granular sheet under a pressure of 50 kg/cm.sup.2 using a roll compactor
TF-MINI (mfg. by Freund Sangyo K. K.) and then broken using pestle and
mortar and screened for obtaining granule having a particle diameter in
the range of 1000-297 .mu.m.
Preparation Example 2
The granule having a particle diameter in the range of 1680-1000 .mu.m was
prepared by the same operation in the same composition as Preparation
Example 1.
Preparation Example 3
The same procedure as in Preparation Example 1 was repeated with 20 parts
of the compound (128), 9 parts of REAX 85A, 1 part of REAX 88B, 5 parts of
GEROPON SC-211, 5 parts of boron oxide, 30 parts of sodium carbonate and
30 parts of maleic acid to give granules having a diameter of 1000-297
.mu.m.
Preparation Example 4
The same procedure as in Preparation Example 1 was repeated with 20 parts
of the compound (128), 11.25 parts of REAX 85A, 1.25 part of REAX 88B, 5
parts of GEROPON SC-211, 2.5 parts of boron oxide, 30 parts of sodium
carbonate and 30 parts of maleic acid to give granules having a diameter
of 1000-297 .mu.m.
Preparation Example 5
The same procedure as in Preparation Example 1 was repeated with 20 parts
of the compound (128), 4.5 parts of REAX 85A, 0.5 part of REAX 88B, 5
parts of GEROPON SC-211, 10 parts of metaboric acid, 30 parts of sodium
carbonate and 30 parts of maleic acid to give granules having a diameter
of 1000-297 .mu.m.
Preparation Example 6
The same procedure as in Preparation Example 1 was repeated with 20 parts
of the compound (128), 9 parts of REAX 85A, 1 part of REAX 88B, 5 parts of
metaboric acid, 5 parts of lactose, 30 parts of sodium carbonate and 30
parts of maleic acid to give granules having a diameter of 1000-297 .mu.m.
Preparation Example 7
The same procedure as in Preparation Example 1 was repeated with 6 parts of
the compound (97), 22.5 parts of REAX 85A, 1.5 parts of REAX 88B, 5 parts
of GEROPON SC-211, 5 parts of boron oxide, 30 parts of sodium carbonate
and 30 parts of maleic acid to give granules having a diameter of 1000-297
.mu.m.
Preparation Example 8
The same procedure as in Preparation Example 1 was repeated with 6 parts of
the compound (97), 22.5 parts of REAX 85A, 1.5 parts of REAX 88B, 5 parts
of GEROPON SC-211, 5 parts of metaboric acid, 30 parts of sodium carbonate
and 30 parts of maleic acid to give granules having a diameter of 1000-297
.mu.m.
Preparation Example 9
The same procedure as in Preparation Example 1 was repeated with 0.2 part
of the compound (126), 31.8 parts of REAX 85A, 3 parts of REAX 88B, 5
parts of boron oxide, 30 parts of sodium carbonate and 30 parts of maleic
acid to give granules having a diameter of 1000-297 .mu.m.
Preparation Example 10
The same procedure as in Preparation Example 1 was repeated with 0.1 part
of the compound (126), 26.9 parts of REAX 85A, 3 parts of REAX 88B, 5
parts of GEROPON SC-211, 5 parts of boron oxide, 30 parts of sodium
carbonate and 30 parts of maleic acid to give granules having a diameter
of 1000-297 .mu.m.
Preparation Example 11
The same procedure as in Preparation Example 1 was repeated with 0.2 part
of the compound (126), 13.5 parts of REAX 85A, 1.5 parts of REAX 88B, 5
parts of boron oxide, 49.8 parts of sodium carbonate and 30 parts of
maleic acid to give granules having a diameter of 1000-297 .mu.m.
Preparation Example 12
The same procedure as in Preparation Example 1 was repeated with 8 parts of
the compound (164), 20.5 parts of REAX 85A, 1.5 parts of REAX 88B, 5 parts
of GEROPON SC-211, 5 parts of boron oxide, 30 parts of sodium carbonate
and 30 parts of maleic acid to give granules having a diameter of 1000-297
.mu.m.
Preparation Example 13
The same procedure as in Preparation Example 1 was repeated with 50 parts
of the compound (155), 13 parts of MORWET D425 (formaldehyde condensate of
sodium naphthalene sulfonate, manufactured by DESOTO), 2 parts of Sorpol
5029-o (sodium alkylsulfate, manufactured by TOHO KAGAKU K. K.), 5 parts
of metaboric acid, 15 parts of sodium bicarbonate and 15 parts of fumaric
acid to give granules having a diameter of 1000-297 .mu.m.
Preparation Example 14
2 parts of the compound (165), 2 parts of polyoxyethylene (20) sorbitan
monolaurate, 10 parts of boron oxide, 40 parts of sodium bicarbonate and
46 parts of maleic acid were mixed with a mortar and a pestle and further
mixed well in a juice mixer. The mixture was next pressed at a pressure of
150 kg/cm.sup.2 with a roll compactor TF-MINI model to form a granulated
sheet, which was then broken with a mortar and a pestle and passed through
a screen to give granules having a particle diameter of 1000-297 .mu.m.
Preparation Example 15
The same procedure as in Preparation Example 14 was repeated with 2 parts
of the compound (165), 2 parts of polyoxyethylene (10) nonyl phenyl ether,
10 parts of boron oxide, 40 parts of sodium bicarbonate and 46 parts of
maleic acid to give granules having a diameter of 1000-297 .mu.m.
Preparation Example 16
The same procedure as in Preparation Example 14 was repeated with 5 parts
of the compound (125), 5 parts of phenylxylylethane, 10 parts of Carplex
CS-7 (a calcined product of silica produced by the wet process,
manufactured by Shionogi & Co., Ltd.), 5 parts of boron oxide, 12 parts of
a spray-dried product of sodium dodecylbenzenesulfonate:Carplex CS-7=1:1
(Carplex CS-7 was dispersed into an aqueous solution of sodium
dodecylbenzenesulfonate and then the mixture was spray-dried with a
spray-dryer to form powder), 3 parts of DEMOL SN-B (formaldehyde
condensate sodium naphthalene sulfonate, manufactured by Kao Soap Co.,
Ltd.), 30 parts of sodium carbonate and 30 parts of maleic acid to give
granules having a diameter of 1000-297 .mu.m.
Preparation Example 17
The same procedure as in Preparation Example 14 was repeated with 5 parts
of the compound (125), 10 parts of phenylxylylethane, 11 parts of Carplex
CS-7, 10 parts of boron oxide, 10 parts of a spray-dried product of sodium
dodecylbenzenesulfonate:Carplex CS-7=1:1, 3 parts of DEMOL SN-B, 21 parts
of lactose, 15 parts of sodium carbonate and 15 parts of maleic acid to
give granules having a diameter of 1000-297 .mu.m.
Preparation Example 18
The same procedure as in Preparation Example 14 was repeated with 5 parts
of the compound (125), 10 parts of phenylxylylethane, 11 parts a Carplex
CS-7, 10 parts of boron oxide, 9 parts of REAX 85A, 1 part of REAX 85B, 5
parts of GEROPON SC-211, 19 parts of lactose, 15 parts of sodium carbonate
and 15 parts of maleic acid to give granules having a diameter of 1000-297
.mu.m.
Preparation Example 19
The same procedure as in Preparation Example 14 was repeated with 5 parts
of the compound (125), 10 parts of phenylxylylethane, 11 parts of Carplex
CS-7, 10 parts of boron oxide, 10 parts of a spray-dried product of sodium
dodecylbenzenesulfonate:Carplex CS-7=1:1, 3 parts of DEMOL SN-B, 5 parts
of polyethylene glycol (average molecular weight, 20000), 16 parts of
calcined diatomite, 15 parts of sodium carbonate and 15 parts of maleic
acid to give granules having a diameter of 1000-2297 .mu.m.
Preparation Example 20
The same procedure as in Preparation Example 14 was repeated with 5 parts
of the compound (125), 10 parts of phenylxylylethane, 11 parts of AEROSIL
200 (silica produced by the dry process, manufactured by Degussa), 10
parts of boron oxide, 9 parts of REAX 85A, 1 part of REAX 85B, 5 parts of
GEROPON SC-211, 19 parts of lactose, 15 parts of sodium carbonate and 15
parts of maleic acid to give granules having a diameter of 1000-297 .mu.m.
Preparation Example 21
The same procedure as in Preparation Example 14 was repeated with 10 parts
of the compound (3), 20 parts of phenylxylylethane, 22 parts of Carplex
CS-7, 5 parts of boron oxide, 10 parts of a spray-dried product of sodium
dodecylbenzenesulfonate:Carplex CS-7=1:1, 3 parts of DEMOL SN-B, 22.5
parts of sodium bicarbonate and 7.5 parts of maleic acid to give granules
having a diameter of 1000-297 .mu.m.
Preparation Example 22
The same procedure as in Preparation Example 14 was repeated with 10 parts
of the compound (3), 20 parts of phenylxylylethane, 22 parts of Carplex
CS-7, 5 parts of boron oxide, 10 parts of a spray-dried product of sodium
dodecylbenzenesulfonate:Carplex CS-7=1:1, 3 parts of DEMOL SN-B, 20 parts
of sodium bicarbonate and 10 parts of maleic acid to give granules having
a diameter of 1000-297 .mu.m.
Preparation Example 23
The same procedure as in Preparation Example 14 was repeated with 10 parts
of the compound (3), 20 parts of phenylxylylethane, 22 parts of Carplex
CS-7, 5 parts of boron oxide, 10 parts of a spray-dried product of sodium
dodecylbenzenesulfonate:Carplex CS-7=1:1, 3 parts of DEMOL SN-B, 15 parts
of sodium bicarbonate and 10 parts of maleic acid to give granules having
a diameter of 1000-297 .mu.m.
Preparation Example 24
The same procedure as in Preparation Example 14 was repeated with 10 parts
of the compound (3), 20 parts of phenylxylylethane, 22 parts of Carplex
CS-7, 5 parts of boron oxide, 10 parts of a spray-dried product of sodium
dodecylbenzenesulfonate:Carplex CS-7=1:1, 3 parts of DEMOL SN-B, 10 parts
of sodium bicarbonate and 20 parts of maleic acid to give granules having
a diameter of 1000-297 .mu.m.
Preparation Example 25
The same procedure as in Preparation Example 14 was repeated with 10 parts
of the compound (3), 20 parts of phenylxylylethane, 22 parts of Carplex
CS-7, 5 parts of boron oxide, 10 parts of a spray-dried product of sodium
dodecylbenzenesulfonate:Carplex CS-7=1:1, 3 parts of DEMOL SN-B, 7.5 parts
of sodium bicarbonate and 22.5 parts of maleic acid to give granules
having a diameter of 1000-297 .mu.m.
Preparation Example 26
The same procedure as in Preparation Example 14 was repeated with 5 parts
of the compound (3), 5 parts of the compound (34), 7 parts of Carplex
CS-7, 5 parts of boron oxide, 10 parts of a spray-dried product of sodium
dodecylbenzenesulfonate:Carplex CS-7=1:1, 3 parts of DEMOL SN-B, 35 parts
of lactose, 15 parts of sodium carbonate and 15 parts of maleic acid to
give granules having a diameter of 1000-297 .mu.m.
Preparation Example 27
A 2.5 g portion of the granule obtained in Preparation Example 1 was placed
in a tableting machine having a diameter of 30 mm and punched at a
pressure of 500 kg/cm.sup.2 to give tablets.
Preparation Example 28
A 5 g portion of the granule obtained in Preparation Example 5 was placed
in a tableting machine having a diameter of 30 mm and punched at a
pressure of 500 kg/cm.sup.2 to give tablets.
Preparation Example 29
A 5 g portion of the granule obtained in Preparation Example 1 was placed
in a tableting machine having a diameter of 30 mm and punched at a
pressure of 500 kg/cm.sup.2 to give tablets.
Preparation Example 30
A 1 g portion of the powder which was intended to be granulated in
Preparation Example 17 was placed in a tableting machine having a diameter
of 20 mm and punched at a pressure of 500 kg/cm.sup.2 to give tablets.
Preparation Example 31
A 0.5 g portion of the powder which was intended to be granulated in
Preparation Example 26 was placed in a tableting machine having a diameter
of 10 mm and punched at a pressure of 300 kg/cm.sup.2 to give tablets.
Preparation Example 32
The same composition as in Preparation Example 1 was used and the same
operations as in Preparation Example 1 were conducted to give granules
having a particle diameter of 4000-297 .mu.m.
Preparation Example 33
The same procedure as in Preparation Example 1 was repeated with 20 parts
of the compound (154), 4.5 parts of REAX 85A, 0.5 part of REAX 88B, 5
parts of GEROPON SC-211, 5 parts of boron oxide, 5 parts of calcium
carbonate, 30 parts of sodium carbonate, and 30 parts of maleic acid to
give granules having a particle diameter of 1000-297 .mu.m.
Preparation Example 34
9 parts of the compounds (128), 8 parts of Carplex CS-7, 5 parts of boron
oxide, 10 parts of a spray-dried product of sodium dodecylbenzene
sulfonate:Carplex CS-7=1:1, 3 parts of DEMOL SN-B, 25 parts of sodium
carbonate, 25 parts of maleic acid and 4.5 parts of lactose were mixed
well in a juice mixer and then pulverized in a centrifugal pulverizer.
After the mixture was placed in a mortar and 10.5 parts of the compound
(123) was added to and mixed with the product with a pestle, the mixture
was mixed well with a juice mixer. The mixture was formed into a
granulated sheet at a pressure of 150 kg/cm.sup.2 with a roll compactor
TF-MINI model, broken with a mortar and a pestle and passed through a
screen to give granules having a particle diameter of 1680-710 .mu.m.
Preparation Example 36
The same composition as in Preparation Example 35 was used and the same
operations as in Preparation Example 35 were conducted to give granules
having a particle diameter of 2000-1000 .mu.m.
Preparation Example 37
The same composition as in Preparation Example 35 was used and the same
operations as in Preparation Example 35 were conducted to give granules
having a particle diameter of 2800-1680 .mu.m.
Preparation Example 38
The same procedure was repeated as in Preparation Example 35 except that 5
parts of metaboric acid was used in place of 5 parts of boron oxide to
give granules having a particle diameter of 1680-710 .mu.m.
Preparation Example 39
The same procedure was repeated as in Preparation Example 35 except that 15
parts instead of 25 parts of sodium carbonate, 15 parts instead of maleic
acid and 24.5 parts instead of 4.5 parts of lactose to give granules
having a particle diameter of 1680-710 .mu.m.
Preparation Example 40
The same procedure was repeated as in Preparation Example 39 except that 5
parts of metaboric acid was used in place of 5 parts of boron oxide to
give granules having a particle diameter of 1680-710 .mu.m.
Preparation Example 41
The same procedure was repeated as in Preparation Example 39 except that 15
parts of boric acid was used in place of 5 parts of maleic acid to give
granules having a particle diameter of 1680-710 .mu.m.
Preparation Example 42
The same procedure was repeated as in Preparation Example 39 except that 15
parts of citric acid was used in place of 5 parts of maleic acid to give
granules having a particle diameter of 1680-710 .mu.m.
Preparation Example 43
The same procedure as in Preparation Example 35 was repeated with 9 parts
of the compound (128), 8 parts of Carplex CS-7, 5 parts of boron oxide, 15
parts of GEROPON SC-211, 25 parts of sodium carbonate, 25 parts of maleic
acid, 2.5 parts of lactose and 10.5 parts of the compound (123) to give
granules having a particle diameter of 1680-71.0 .mu.m.
Preparation Example 44
The same procedure as in Preparation Example 35 was repeated with 9 parts
of the compound (123), 8 parts of Carplex CS-7, 10 parts of boron oxide,
15 parts of GEROPON SC-211, 15 parts of sodium carbonate, 15 parts of
maleic acid, 17.5 parts of lactose and 10.5 parts of the compound (123) to
give granules having a particle diameter of 1680-710 .mu.m.
Comparative Examples are described below.
Comparative Example 1
The same procedure as in Preparation Example 1 was repeated with 20 parts
of the compound (82), 9 parts of REAX 85A, 1 part of REAX 85B, 10 parts of
lactose, 30 parts of sodium carbonate and 30 parts of maleic acid to give
granules having a particle diameter of 1000-297 .mu.m.
Comparative Example 2
The same procedure as in Preparation Example 1 was repeated with 0.2 part
of the compound (126), 36.8 parts of REAX 85A, 3 parts of REAX 85B, 30
parts of sodium carbonate and 30 parts of maleic acid to give granules
having a particle diameter of 1000-297 .mu.m.
Comparative Example 3
The same procedure as in Preparation Example 1 was repeated with 20 parts
of the compound (154), 5 parts of GEROPON SC-211, 30 parts of sodium
carbonate and 30 parts of maleic acid to give granules having a particle
diameter of 1000-297 .mu.m.
Comparative Example 4
The same procedure as in Preparation Example 14 was repeated with 5 parts
of the compound (125), 5 part of phenylxylylethane, 11 parts of Carplex #8
(an uncalcined silica produced by the wet process, manufactured by
Shionogi & Co., Ltd.), 10 parts of Sorpol 5060 (a spray-dried product of
sodium dodecylbenzene sulfonate:powderous hydric silicic acid=1:1, Toho
Kagaku K. K.), 3 parts of DEMOL SN-B, 31 parts of lactose, 15 parts of
sodium carbonate and 15 parts of maleic acid to give granules having a
diameter of 1000-297 .mu.m.
Comparative Example 5
The same procedure as in Preparation Example 14 was repeated with 10 parts
of the compound (3), 20 parts of phenylxylylethane, 22 parts of Carplex
#8, 10 parts of Sorpol 5060, 3 parts of DEMOL SN-B, 22.5 parts of sodium
carbonate and 7.5 parts of maleic acid to give granules having a diameter
of 1000-297 .mu.m.
Comparative Example 6
The same procedure as in Preparation Example 14 was repeated with 10 parts
of the compound (3), 20 parts of phenylxylylethane, 22 parts of Carplex
#8, 5 parts of lactose, 10 parts of Sorpol 5060, 3 parts of DEMOL SN-B, 20
parts of sodium bicarbonate and 10 parts of maleic acid to give granules
having a diameter of 1000-297 .mu.m.
Comparative Example 7
The same procedure as in Preparation Example 14 was repeated with 10 parts
of the compound (3), 20 parts of phenylxylylethane, 22 parts of Carplex
#8, 5 parts of lactose, 10 parts of Sorpol 5060, 3 parts of DEMOL SN-B, 15
parts of sodium bicarbonate and 15 parts of maleic acid to give granules
having a diameter of 1000-297 .mu.m.
Comparative Example 8
The same procedure as in Preparation Example 14 was repeated with 10 parts
of the compound (3), 20 parts of phenylxylylethane, 22 parts of Carplex
#8, 5 parts of lactose, 10 parts of Sorpol 5060, 3 parts of DEMOL SN-B, 10
parts of sodium bicarbonate and 20 parts of maleic acid to give granules
having a diameter of 1000-297 .mu.m.
Comparative Example 9
The same procedure as in Preparation Example 14 was repeated with 10 parts
of the compound (3), 20 parts of phenylxylylethane, 22 parts of Carplex
#8, 5 parts of lactose, 10 parts of Sorpol 5060, 3 parts of DEMOL SN-B,
7.5 parts of sodium bicarbonate and 22.5 parts of maleic acid to give
granules having a diameter of 1000-297 .mu.m.
Comparative Example 10
4 parts of the compound (128), 4 parts of Sorpol 5060, 30 parts of
bentonite clay and 62 parts of kaolin clay were mixed well in a juice
mixer and then pulverized in a centrifugal pulverizer. Then, 15 parts of
water was added to the mixture, and the resulting mixture was kneaded with
a mortar and a pestle, subjected to granulation and screening in an
extrusion granulator equipped with a screen having a diameter of 0.9 mm
and dried at 60.degree. C. for 10 minutes to give particles having a
particle diameter of 1680-297 .mu.m.
Comparative Example 11
1 part of the compound (165) and 2 parts of Sorpol 3598 (surface active
agent, manufactured by Toho Kagaku K. K.) were mixed, then added to 97
parts of ISHIKAWA LITE #3 (porous granular carrier, manufactured by
Ishikawa LITE K. K.) and mixed well to give particles.
Comparative Example 12
The same procedure as in Preparation Example 14 was repeated with 10 parts
of the compound (3), 20 parts of phenylxylylethane, 22 parts of Carplex
#80, 35 parts of lactose, 10 parts of Sorpol 5060 and 3 parts of Demol
SN-B to give granules having a particle diameter of 1000-297 .mu.m.
Comparative Example 13
The same procedure as in Preparation Example 1 was repeated with 20 parts
of the compound (128), 9 parts of REAX 85A, 1 part of REAX 85B, 10 parts
of anhydrous sodium sulfate, 30 parts of sodium carbonate and 30 parts of
maleic acid to give granules having a particle diameter of 1000-297 .mu.m.
Test Examples are described below.
Test Example 1
About 1 g of each composition obtained in Preparation Examples 1-31, 33 and
34 and Comparative Examples 1-9 and 13 was packed in a
polyethylene-laminated aluminium bag (length, 11.5 cm; width, 16.5 cm) and
stored at 40.degree. C. for 30 days and at 50.degree. C. for 30 days, and
the state of the bag was observed.
After store, the bag was opened by cutting it with scissors to get the gas
generated out of the bag, and the total weight was measured to calculate
the weight loss with the total weight and the weight of the formulation
before storage by the following equation:
##EQU1##
TABLE 1
______________________________________
After storage at
After storage at
40.degree. C. for 30 days
50.degree. C. for 30 days
Test State Weight State Weight
Composition
of bag loss (%) of bag
loss (%)
______________________________________
Preparation
Example
1 - 0 - 0
2 - 0 - 0
3 - 0 - 0.1
4 - 0 - 0.2
5 - 0 - 0.2
6 - 0 - 0.2
7 - 0 - 0
8 - 0
9 - 0
10 - 0
11 - 0.1
12 - 0
13 - 0
14 - 0
15 - 0
16 - 0 - 0.2
17 - 0 - 0.2
18 - 0 - 0.1
19 - 0 - 0.2
20 - 0 - 0
21 - 0 - 0
22 - 0 - 0
23 - 0 - 0.2
24 - 0 - 0.1
25 - 0 - 0.1
26 - 0
27 - 0 - 0
28 - 0
29 - 0
30 - 0 - 0.1
31 - 0
33 - 0.1
34 - 0
Comparative
Example
1 + 0.4 +++ 1.0
2 + 0.6
3 + 0.6
4 +++ 1.2 +++ 3.4
5 + 0.4 + 0.6
6 + 0.6 + 0.8
7 +++ 0.8 +++ 2.0
8 + 0.6 +++ 1.4
9 + 0.6 +++ 1.2
13 + 0.3 +++ 1.0
______________________________________
(Indices for indicating the states of the bag)
-: No change,
+: Slight expansion of bag,
++: Some expansion of bag,
+++: Largely expansion of bag.
Test Example 2
Three partition plates were arranged in an aluminium vat having a length of
35 cm and a width of 53 cm as shown in FIG. 1, and 7 liters of deionized
water was charged in it. Next, the composition obtained in Preparation
Example 3 having a content of the active ingredient corresponding to 100
g/10 are, the aforementioned composition having been stored under the
condition described in Test Example 1, and the composition obtained in
Comparative Example 10 were charged into the vat, respectively, and the
distance of the movement of the composition was observed visually.
After 24 hours from the charge of the compositions, 25 ml of the liquid at
the positions of the distances of 0 cm, 87 cm or 174 cm and at the depth
of about 0.5 cm from the bottom was sampled with a transfer pipet, and
water was evaporated. The residual sample was analyzed by a gas
chromatograph (detector: ECD) to measure the amount of active ingredient.
The results are shown in Table 2.
TABLE 2
______________________________________
Amount of active
ingredient in 25 ml
Dispers-
of liquid (.mu.m)
Test Composition
ibility 0 cm 87 cm 147 cm
______________________________________
Preparation Example 3
A 58.1 67.5 47.0
(immediately after
production)
Preparation Example 3
A 55.0 77.4 55.7
(after storage at
40.degree. C. for 50 days)
Preparation Example 3
A 50.3 54.6 46.5
(after storage at
50.degree. C. for 50 days)
Comparative Example 10
D 84.0 11.4 1.9
______________________________________
(Evaluation criteria of dispersibility)
Shift at a distance of 2 m or more: A, 1 m or more and less than 2 m: B,
50 cm or more and less than 1 m: C, less than 50 cm: D.
It is obvious from Table 2 that the composition of the present invention is
excellent in dispersibility as compared with the conventional preparations
illustrated by Comparative Examples and that the composition of the
present invention is excellent in stability during storage.
Test Example 3
Into an aluminium vat used in Test Example 2 was poured the composition
obtained in Preparation Examples 1, 2, 5, 7, 9 or 12 in an amount which
corresponds to 750 g of the composition per 10 are. The distance of the
movement of the composition was observed visually and its dispersibility
was evaluated.
The results are listed in Table 3 (using the same evaluation criteria for
dispersibility)
TABLE 3
______________________________________
Test composition Dispersibility
______________________________________
Preparation Example 1
A
Preparation Example 2
A
Preparation Example 5
A
Preparation Example 7
A
Preparation Example 9
A
Preparation Example 12
A
______________________________________
Test Example 4
To the water surface around the root of a rice at a tillering period
planted in a Wagner pot having an area of 1/10000 are was applied the
composition obtained in Preparation Examples 14 and 15 and Comparative
Example 11 in an amount of the active ingredient corresponding to 30 g/10
are. This was covered with a metal net basket, of which external side was
covered with a polyethylene bag, in which 15 brown rice planthoppers were
pastured and their life or death was examined after 24 hours.
TABLE 4
______________________________________
Mortality of brown
Test composition
rice plant hopper (%)
______________________________________
Preparation 100
Example 14
Preparation 97
Example 15
Comparative 36
Example 11
______________________________________
Test Example 5
Self dispersibilities of the compositions obtained in Preparation Example
23 and Comparative Example 7, those having been stored under the condition
described in Test Example 1 and the composition obtained in Comparative
Example 12 were measured by the following method. In this connection, the
self-dispersibility indicates the suspension rate of the active ingredient
in the state without stirring.
A 250 ml volume cylinder with a co-stopper containing 250 ml of water
having 3 H (hardness) at 20.degree. C. was placed and 500 mg of each
composition was charged through a funnel into the cylinder. A 25 ml
portion of the sample was taken out of the center of the cylinder at 2 mm
after dilution, the gas chromatographical analysis (detector: FID) was
conducted to evaluate the self-dispersibility after water was evaporated.
The results are shown in Table 5.
TABLE 5
______________________________________
Self-dispersibility (%)
Immediately After storage
After storage
Test after pro- at 40.degree. C.
at 50.degree. C.
Composition
duction 30 days 30 days
______________________________________
Preparation
88.5 91.5 85.5
Example 23
Comparative
78.9 62.0 53.3
Example 7
Comparative
5.3 -- --
Example 12
______________________________________
It is obvious from Table 5 that the composition of the present invention
are excellent in self-dispersibility as compared with the
non-effervescence composition described in Comparative Example 12 and are
also excellent in storage stability as compared with the foaming
composition described in Comparative Example 7.
In the accompanying drawing:
FIG. 1 is a plan view of an aluminium vat used in Experimental Examples 2
and 3, wherein three partitions are provided so that they are parallel to
the longer side walls of the vat and the gap between the partitions and
the shorter side walls is 9 cm. The mark X indicates the position at which
the test composition is charged.
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